Indophenolic compound and process of making same.



* UNITED STATES PATENT OFFICE.

RICHARD HEBZ, or FRANKFORT-ON-THE-MAIN, GERMANY, ASSIEGNOR. T0 CASSELLA COLOR ooMPAN'g, on NEW YORK, N. Y.

INDOPHENOLIC COMPOUND AND PROCESS OF MAKING SAME.

No Drawing.

. Specification of Letters Patent.

Patented Aug. 2, 1910.

Application filed March 4, 1910. Serial No. 547,212.

. dyestufls, derived from -(N) substituted 1 derivatives of carbazole.

I have'discovered that by condensing p. nitrosophenol and analogous compounds with derivatives of carbazole, substituted in the .imido group, viz. the N. alkyl or N.

arylcarbazole, preferably in presence of concentrated sulfuric acid, new products of condensation are produced, showing the properties ofindo henols. These new substances have. probab y the following general formula Y in which R means: (1) the alk 1 group, viz. the .methyl-, ethyl roup, viz. the phenfy onicgroup, etc. I (t densatlon, or their leuco compounds be- $011!). 2)- the aryl ben zylp. -tolylsullieseproducts of conheated withalkalinepolysulfids, new dyestuffs containing sulfur'in their molecule,

. Oh emie, Vol. 202, page 23, the hitherto-un-f are obtained, dyeing vegetable fibers indigo I blue to pure blue shades which possess excellent fastness to washing, lightand bleachin c Theproduction of methyland ethyl-car'- bazole is described" inthe Amr'alen der known aryl-carbazoles are obtained in an analogous manner. For instance (N benzyl-carbazole is obtained by heating t e otassium salt of carbazole with benzyl-ch orid;it is insoluble in water, difiicultly so1-' uble incold, morev easily in-hot alcohol and.

crystallizes from the latter in the form of colorless needles with a meltingoint of 118 v to 120 C. The (N.) phenyl-carazole crys-' sop/renal and (N.)

tallizes from hot alcohol in' colorless needles with a melting point of 8-2 to 84 C.

The process of working of my invention is illustrated by the following examples:

Emample 1-00ndensatz'0n of p. nitroetkyl-carbazole.19.5 kilos of ethyl-carbazole are dissolved in about 200 kilos of cold concentrated sulfuric acid of 66 B.

To this is added,

while stirring and cooling well, a solution of 12.3 kilos of p. nitrosophenol in about ten times its weight of concentrated sulfuric acid. Preferably the temperature of the mixed solutions isvnot allowed to rise above 10 C. -When the reaction is complete, the

whole is poured on to ice, the se arated prod uct of condensation is filtered o and washed with water until it shows a. neutral reaction. For the production of sulfid dyestuffs this product of condensation may be used as it is, or it may be reduced to the leuco compound 1 vby the usual methods; both the indophenols and their leuco compounds may be purified by extracting the raw products with suitable, solvents, such asv for instance hot'alcohol which dissolves the pure-bodies, but leaves the impurities undissolved.

The indophenolsare in a drystate dark blue powders, insoluble in water, dilute acids and alkalies, but soluble with'a blue violet color in methyl alcohol, with a reddishviolet color in chloroform, andwith ama-' genta-red color in acetone. The leuco-indophenols are in a dry state crystalline gray ish-white powders, insoluble in water, easily soluble in hot dilute caustic alkalies and also in sodium sulfid solution. I 9 Y The manufacture of the dyestufi's may be efiected by the usual methods of sulfurizing," for instance by heatin the substances with alkalineolysulfids, eit er in an aqueous solution w1' h, or without the addition'of glyc 'erin, or in an alcoholic solution, or by melting the leuco bases with sulfur. The shades andproperties of the resulting coloring matters vary according to the conditions of manufacture. Asa rule, if the usual methods of sulfurizing be ap lied, blue dyestufls result, possessing all t e typical pro erties of the well-known sulfid dyestuflf's. the alka ine polysulfid t-if for roduction of thecoloring. matters an Y used,-' containing a' high percentage of sulfur, and further on, if the process be effected in presence of a suitable solvent for the indophenol or leucoindophenol, preferably in an alcoholic solution, then almost exclusively dyestuffs result which are practically insoluble in dilute alkaline sulfid solution. These coloring matters can be reduced by a warm solution of alkaline hydrosulfite to a yellowish colored vat, and dye cotton in such a vat indigo-blue to pure-blue shades which exceed in their fastness to washing, light and bleaching, those produced with indigo.

E wample 2P1"oduetz'on of a blue oat dyestufi', derived from the indoplzenol, 07* leucoz'mlophenol, derived from p. m'trosophenol and ethyl-earbaeOZe-SO kilos of sodium sulfid 160 kilos of finely ground sulfur, preferably flower of sulfur and 400 liters of alcohol are heated for several hours in a vessel provided with a reflux condenser, until the alkaline polysulfid is formed. Then 40 kilos of the pure, dry indophenol, derived from p. nitrosophenol and (N.) ethyl carbazole, or the equivalent amount of the leuco base are added, and the heating is continued for about 48 hours. When the reaction is complete, the alcohol is distilled off and the residue diluted with water and filtered. The product thus obtained is then digested with a solution of sodium sulfid crystals whereby the superfluous sulfur and the small amounts of byproducts, easily soluble in sodium sulfid soution, are dissolved. It is then filtered again and washed with water. The undissolved residue representing the pure vat dyestuff, if dried, is a dark blue powder with a metallic luster, almost insoluble in the usual organic solvents, soluble with a blackblue color in concentrated sulfuric acid, practically insoluble in dilute alkaline sulfid solution, but soluble with a 'pure yellow color in warm alkaline hydrosulfite solution, forming a vat and dyeing cotton in such a vat greenish-blue to bright blue shades fast to washing, light and bleaching.

Having now particularly described and ascertained the nature of my said invention andin what manner the same is to be performed, I declare that what I claim, is:

1'. The process of making indophenolic compounds by condensing p. nitrosophenols with a derivative of carbazole substituted in the imido group, substantially as described.

2. The process of making fast blue dyestuffs which consists in condensing p. nitrosophenol's with a derivative ofcarbazole subee aoea nitrosophenols and derivatives of carbazole,

substituted in the imido group being in a dry state dark blue powders insoluble in water, dilute acids, and alkalies, soluble with a blue violet color in methyl-alcohol, with a reddish violet color in chloroform, with a magenta-red color in acetone and forming leuco compounds, if treated with the usual reducing agents, substantially as described.

-5. As a new article of manufacture the fast blue sulfid dyestuffs derived from p. nitrosophenols and derivatives of carbazole substituted in the imido group being in a dry state dark blue powders with a'metallic aspect, insoluble in water and alcohol, soluble with a bright blue color in hot phenol, easily soluble in an alkaline sulfid solution and dyeing from such a bath cotton fast indigo blue to bright blue shades, substantially asdescribed.

6. As a new article of manufacture the fast blue vat dyestuffs derived from p. nitrosophenols and derivatives of carbazole, substituted in the imido group being in a dry state dark blue powders with a metallic aspect, insoluble in the usual organic solvents, soluble with a dark blue color in concentrated sulfuric acid, practically insoluble in a dilute alkaline sulfid solution, but soluble with a pure yellow color in warm alkaline hydrosulfite solutions forming a vat and dyeing cotton in such a vat indigo blue to bright blue shades fast to washing, light and bleaching, substantially as described.

In witness whereof I have hereunto signed my name this 21st day of February 1910, in the presence of two subscribing witnesses.

RICHARD HERZ.

Witnesses JEAN GRUND, CARL GRUND. 

